US6391923B1 - Aqueous polymer dispersion, its preparation and use - Google Patents

Aqueous polymer dispersion, its preparation and use Download PDF

Info

Publication number
US6391923B1
US6391923B1 US09/615,422 US61542200A US6391923B1 US 6391923 B1 US6391923 B1 US 6391923B1 US 61542200 A US61542200 A US 61542200A US 6391923 B1 US6391923 B1 US 6391923B1
Authority
US
United States
Prior art keywords
water
aqueous dispersion
vinyl
polymerization
alkylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US09/615,422
Inventor
Klaus Pöllmann
Hendrik Ahrens
Achim Stankowiak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19939266A external-priority patent/DE19939266B4/en
Application filed by Clariant GmbH filed Critical Clariant GmbH
Assigned to CLARIANT GMBH reassignment CLARIANT GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AHRENS, HENDRIK, POLLMANN, KLAUS, STANKOWIAK, ACHIM
Priority to US10/103,903 priority Critical patent/US20020103290A1/en
Application granted granted Critical
Publication of US6391923B1 publication Critical patent/US6391923B1/en
Assigned to CLARIANT PRODUKTE (DEUTSCHLAND) GMBH reassignment CLARIANT PRODUKTE (DEUTSCHLAND) GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: CLARIANT GMBH
Adjusted expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C08F216/1425—Monomers containing side chains of polyether groups
    • C08F216/1433—Monomers containing side chains of polyethylene oxide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1458—Monomers containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements

Definitions

  • the present invention relates to polymer dispersions which can be prepared using polymerizable polyalkylene glycol macromonomers.
  • the polymeric emulsifiers and protective colloids used for very diverse applications are generally ambivalent copolymers which contain both hydrophobic and hydrophilic comonomer fractions.
  • a typical example is the partially hydrolyzed polyvinyl acetate used in the suspension polymerization of, for example, styrene, disclosed, for example, in W. P. J.
  • Copolymers of acrylic acid and hydrophobic acrylic and methacrylic esters such as, for example, dodecyl methacrylate, which are used in the cosmetics sector to formulate and stabilize aqueous lotions and emulsions of water-insoluble oils (lit: BF Goodrich product information “Pemulen Emulsifiers” 1995), or acrylic copolymers, which are used to stabilize aqueous dispersions of silicates, gypsum, talc, clay and other minerals in the exploration of petroleum and formulation of building materials (EP-A-0 870784), act in a similar way.
  • acrylic acid and hydrophobic acrylic and methacrylic esters such as, for example, dodecyl methacrylate
  • JP-A-5-209 052 discloses copolymers of vinyl chloride with vinyl polyether macromonomers which are produced in the form of solid products. A dispersing action of the vinyl polyether macromonomers is not disclosed.
  • EP-A-0 736 553 discloses copolymers of carboxylic acids or derivatives thereof and propoxylated vinyl ethers, but these too do not form a dispersion.
  • the object of the present invention was to find a process with which copolymers can be directly obtained as aqueous dispersions.
  • the present invention describes a class of water-dispersed copolymers which can be prepared by copolymerizing allyl or vinyl polyethers with known, mostly hydrophobic monomers.
  • the copolymers can be used without a diluent for the emulsification/dispersion, or, depending on the process and intended use, such as, for example, in the case of emulsion polymerization, can be prepared in situ by adding small amounts of the polymerizable macromonomers.
  • the invention thus provides aqueous dispersions preparable by polymerization of an olefinically unsaturated, water-insoluble compound in the presence of a water-soluble allyl or vinyl ether of the formula 1
  • b 0 or 1
  • n 0 or1
  • k is an integer from 1 to 20,
  • X is O or N[(A—O) m —R]
  • A is C 2 -C 4 -alkylene
  • R is H or C 1 -C 4 -alkyl
  • A is not exclusively C 3 - or C 4 -alkylene
  • k preferably assumes values from 2 to 12, in particular 4 to 8.
  • X is preferably oxygen.
  • R is preferably hydrogen.
  • A is preferably an ethylene or propylene radical, in particular an ethylene radical.
  • the total number of alkoxy units is preferably between 8 and 240, in particular between 16 and 115.
  • the alkoxy chain can be a block polymer chain which has alternating blocks of different alkoxy units, preferably ethoxy and propoxy units. It can also be a chain with alkoxy units in random sequence.
  • —(A—O) m — is an alkoxy chain of the formula
  • a is a number from 0 to 300, preferably 1 to 80, in particular 2 to 35
  • b is a number from 5 to 300, preferably 8 to 80, in particular 10 to 45
  • c is a number from 0 to 300, preferably 8 to 80, in particular 8 to 35.
  • —(A—O) m — is an ethoxy radical having from 8 to 240 ethoxy units.
  • a common feature of all of the embodiments is that preferably at least 50 mol % of the radicals (A—O) are ethoxy radicals, in particular 60 to 90 mol % are ethoxy radicals.
  • the number of propoxy and butoxy radicals is, in a preferred embodiment, at most so great that the cloud point of the compound of the formula 1 in water is still at 30° C. or above.
  • the compounds of the formula 1 are also referred to below as polymerizable macromonomers.
  • the polymerizable macromonomers are prepared by anion/alkali initiated polymerization of hydroxy- or amino-functional allyl or vinyl ethers (ethers which still have at least one active hydrogen atom) with alkylene oxide or mixtures of alkylene oxides in random distribution or as block copolymers. Furthermore, the resulting macromonomers can also be etherified at the terminal hydroxyl groups by means of a Williamson synthesis.
  • the hydroxy- or amino-functional allyl or vinyl ethers have formula 3
  • the degree of water solubility, defined by the cloud point, of the polymerizable macromonomers, and the extent of their hydrophilicizing and dispersing action can be set by the ratio and number of alkylene oxide units, preferably of ethylene oxide to propylene oxide, and through the choice of the hydroxy- or amino-functional allyl or vinyl ether.
  • Suitable water-insoluble monomers which can be polymerized with the macromonomers are, for example, the following:
  • vinyl monomers such as carboxylic esters of vinyl alcohol, for example vinyl acetate, vinyl propionate, vinyl ether of isononanoic acid or of isodecanoic acid, styrene and stilbene,
  • olefinically unsaturated carboxylic esters such as ethyl acrylate, n-butyl acrylate, i-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, and the corresponding methacrylic esters,
  • olefinically unsaturated carboxylic acids such as acrylic acid, methacrylic acid and itaconic acid and their sodium, potassium and ammonium salts,
  • olefinically unsaturated sulfonic acids and phosphonic acids and their alkali metal and ammonium salts such as acrylamidomethylpropanesulfonic acid (AMPS) and its alkali metal and ammonium, alkylammonium and hydroxyalkylammonium salts, allylsulfonic acid and its alkali metal and ammonium salts, acryloyloxethylphosphonic acid and its ammonium and alkali metal salts, and the corresponding methacrylic acid derivatives,
  • AMPS acrylamidomethylpropanesulfonic acid
  • alkylammonium and hydroxyalkylammonium salts alkylammonium and hydroxyalkylammonium salts
  • allylsulfonic acid and its alkali metal and ammonium salts acryloyloxethylphosphonic acid and its ammonium and alkali metal salts
  • olefinically unsaturated amines such as dimethylaminoethyl acrylate, acryloyloxethyltrimethylammonium halides, acrylonitrile, N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, and the corresponding methacrylic acid derivatives and vinylmethylacetamide,
  • olefins such as ethylene, propene and butenes, pentene, 3-butadiene and chloroprene,
  • vinyl halides such as vinyl chloride, vinylidene chloride and vinylidene fluoride.
  • the present invention further relates to the use of the above-defined macromonomers of the formula 1 in emulsion polymerizations or suspension polymerizations.
  • the invention further provides for the use of the polymerizable polyalkylene macromonomers according to the invention as emulsifiers or dispersants.
  • the compounds of the formula 1 can be used in suspension or emulsion polymerizations alone as emulsifiers, and also in a mixture with anionic and/or nonionic surfactants known in the prior art.
  • Customary anionic surfactants are sodium alkyl sulfate, sodium dodecylbenzenesulfonate, sodium alkylsulfonate, sodium and ammonium alkylpolyethylene glycol ether sulfates, sodium and ammonium alkylphenol polyethylene glycol ether sulfates, and alkylpolyethylene glycol ether phosphoric mono-, di- and triesters and mixtures thereof, and alkylphenol polyethylene glycol ether phosphoric mono-, di- and triesters and mixtures thereof.
  • the macromonomer from Example 1 is copolymerized with AMPS.
  • the macromonomer from Example 2 is used as coemulsifier in the emulsion polymerization of vinyl acetate and vinyl isodecanoate.
  • the copolymer of vinyl acetate and vinyl isodecanoate and the macromonomer from Example 2 which forms in situ has good emulsion-stabilizing properties because of its ambivalent structure.
  • the mixture is then heated up to 76° C. and, after the reaction has started at 80° C., the remaining monomer emulsion and a further 210 g of a 1.17% strength ,potassium peroxodisulfate solution are metered in over 3 hours.
  • the mixture is then stirred for 2 hours for after polymerization at 80° C. and cooled to room temperature. During the cooling phase, 3 g of preservative (200 Mergal K9N) are added.
  • the macromonomer from Example 2 is used as coemulsifier in the emulsion polymerization of n-butyl acrylate, methyl methacrylate and methacrylic acid.
  • the copolymer of n-butyl acrylate, methyl methacrylate and methacrylic acid and the macromonomer from Example 2 which forms in situ has good emulsion-stabilizing properties on the basis of its ambivalent structure.
  • 520 ml of water are charged to a glass flask, and 16 g of ®Emulsogen EPA 1954 (sodium alkyl sulfate), 15 g of a 3.75% strength ammonium peroxodisulfate solution, 11.8 g of n-butyl acrylate, 11.8 g of methyl methacrylate and 0.48 g of methacrylic acid are added, and the mixture is stirred. The emulsion is heated to 80° C.
  • a monomer emulsion which consists of 475 ml of water, 16 g of Emulsogen EPA 1954, 4.8 g of the macromonomer from Example 2, 440 g of n-butyl acrylate, 440 g of methyl methacrylate, 8.8 g of methacrylic acid and 2.85 g of ammonium peroxodisulfate is metered in over 4 hours.
  • the polymer dispersion is cooled to room temperature and adjusted to pH 8-9 using ammonia solution.
  • the macromonomer consisting of a block polymer of allyl alcohol, Which has been reacted firstly with 5 mol of propylene oxide and then with 30 mol of ethylene oxide, is used as coemulsifier in the emulsion polymerization of n-butyl acrylate, methyl methacrylate and methacrylic acid.
  • the copolymer of n-butyl acrylate, methyl methacrylate and methacrylic acid and the described allyl alkoxide which forms in situ has good emulsion-stabilizing properties on the basis of its ambivalent structure.
  • 520 ml of water are charged to a glass flask, and 16 g of ®Emulsogen EPA 1954 (sodium alkyl sulfate), 15 g of a 3.75% strength ammonium peroxodisulfate solution, 11.8 g of n-butyl acrylate, 11.8 g of methyl methacrylate and 0.48 g of methacrylic acid are added, and the mixture is stirred. The emulsion is heated to 80° C.
  • a monomer emulsion which consists of 460 ml of water, 32 g of Emulsogen EPA 1954, 4.8 g of the described allyl alkoxylate, 440 g of n-butyl acrylate, 440 g of methyl methacrylate, 8.8 g of methacrylic acid and 2.85 g of ammonium peroxodisulfate, is metered in over 4 hours.
  • the polymer dispersion is cooled to room temperature and adjusted to pH 8-9 using ammonia solution.
  • Example 2 To 100 g of the product from Example 1 are added, under nitrogen, firstly 10 g of solid NaOH, and then 14 g of n-butyl chloride are metered in. The reaction vessel is stirred at superatmospheric pressure for 5 hours at 80° C. The vessel is then evacuated and heated under reduced pressure to 120° C. and stirred for a further 3 hours.
  • the reaction mixture After the reaction mixture has cooled, it is repeatedly stirred with 500 ml of water and left to stand to enable the phases to separate. The aqueous sodium-chloride-containing phase is discarded in each case.
  • the upper phase (yield: 94 g/88%) is, according to 1 H-NMR, iodine number determination (24 g/100 g) and OH number measurement (5 mg/g), finally the mono-n-butylpolyethylene glycol mono-4-hydroxyvinyl ether having 18 units of ethylene oxide.
  • Example 2 To 100 g of the product from Example 1 are added, under nitrogen in an autoclave, firstly 10 g of solid NaOH, and then 7 g of methyl chloride are metered in under superatmospheric pressure. The reaction vessel is stirred at superatmospheric pressure for 5 hours at 80° C. The vessel is then evacuated and heated under reduced pressure to 120° C. and stirred for a further 3 hours.
  • the reaction mixture After the reaction mixture has cooled, it is repeatedly stirred with 500 ml of water and left to stand to enable the phases to separate. The aqueous sodium-chloride-containing phase is discarded in each case.
  • the upper phase (yield: 92 g/90%) is, according to 1 H-NMR, iodine number determination (26 g/100 g) and OH number measurement (5 mg/g), finally the mono-methyl polyethylene glycol mono4-hydroxyvinyl ether having 18 units of ethylene oxide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyethers (AREA)
  • Polymerisation Methods In General (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to aqueous dispersions preparable by polymerization of an olefinically unsaturated, water-insoluble compound in the presence of a water-soluble allyl or vinyl ether of the formula 1
Figure US06391923-20020521-C00001
in which
b is 0 or 1
n is 0 or 1
k is an integer from 1 to 20,
X is O or N[(A—O)m—R]
A is C2-C4-alkylene
m is an integer from 5 to 900, and
R is H or C1-C4-alkyl,
and in which A is not exclusively C3- or C4-alkylene, by mixing the olefinically unsaturated water-insoluble compound with the water-soluble allyl and vinyl ether in water, and triggering the polymerization by a free-radical initiator.

Description

BACKGROUND OF THE INVENTION
The present invention relates to polymer dispersions which can be prepared using polymerizable polyalkylene glycol macromonomers.
The polymeric emulsifiers and protective colloids used for very diverse applications are generally ambivalent copolymers which contain both hydrophobic and hydrophilic comonomer fractions. A typical example is the partially hydrolyzed polyvinyl acetate used in the suspension polymerization of, for example, styrene, disclosed, for example, in W. P. J. Bailey in Chemistry and Technology of water-soluble Polymers, Plenum Press, 1983 page 261 et seq., ISBN 0306-41251-9, which adsorbs via the nonhydrolyzed fractions of vinyl acetate to the emulsified styrene droplets and, via the hydrophilic fractions of polyvinyl alcohol, ensures emulsification of these droplets in the aqueous suspension. Copolymers of acrylic acid and hydrophobic acrylic and methacrylic esters, such as, for example, dodecyl methacrylate, which are used in the cosmetics sector to formulate and stabilize aqueous lotions and emulsions of water-insoluble oils (lit: BF Goodrich product information “Pemulen Emulsifiers” 1995), or acrylic copolymers, which are used to stabilize aqueous dispersions of silicates, gypsum, talc, clay and other minerals in the exploration of petroleum and formulation of building materials (EP-A-0 870784), act in a similar way.
DESCRIPTION OF THE RELATED ART
JP-A-5-209 052 discloses copolymers of vinyl chloride with vinyl polyether macromonomers which are produced in the form of solid products. A dispersing action of the vinyl polyether macromonomers is not disclosed.
EP-A-0 736 553 discloses copolymers of carboxylic acids or derivatives thereof and propoxylated vinyl ethers, but these too do not form a dispersion.
SUMMARY OF THE INVENTION
The object of the present invention was to find a process with which copolymers can be directly obtained as aqueous dispersions.
The present invention describes a class of water-dispersed copolymers which can be prepared by copolymerizing allyl or vinyl polyethers with known, mostly hydrophobic monomers. The copolymers can be used without a diluent for the emulsification/dispersion, or, depending on the process and intended use, such as, for example, in the case of emulsion polymerization, can be prepared in situ by adding small amounts of the polymerizable macromonomers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention thus provides aqueous dispersions preparable by polymerization of an olefinically unsaturated, water-insoluble compound in the presence of a water-soluble allyl or vinyl ether of the formula 1
Figure US06391923-20020521-C00002
in which
b is 0 or 1
n is 0 or1
k is an integer from 1 to 20,
X is O or N[(A—O)m—R]
A is C2-C4-alkylene
m is an integer from 5 to 900, and
R is H or C1-C4-alkyl,
and in which A is not exclusively C3- or C4-alkylene, by mixing the olefinically unsaturated water-insoluble compound with the water-soluble allyl or vinyl ether in water, and triggering the polymerization by a free-radical initiator.
k preferably assumes values from 2 to 12, in particular 4 to 8. X is preferably oxygen. R is preferably hydrogen. In a further preferred embodiment n=1, b=0 and X=O.
In the alkoxy chain given by (A—O)m, A is preferably an ethylene or propylene radical, in particular an ethylene radical. The total number of alkoxy units is preferably between 8 and 240, in particular between 16 and 115. The alkoxy chain can be a block polymer chain which has alternating blocks of different alkoxy units, preferably ethoxy and propoxy units. It can also be a chain with alkoxy units in random sequence.
In a preferred embodiment, —(A—O)m— is an alkoxy chain of the formula
Figure US06391923-20020521-C00003
in which
a is a number from 0 to 300, preferably 1 to 80, in particular 2 to 35
b is a number from 5 to 300, preferably 8 to 80, in particular 10 to 45
c is a number from 0 to 300, preferably 8 to 80, in particular 8 to 35.
In a further preferred embodiment, —(A—O)m— is an ethoxy radical having from 8 to 240 ethoxy units.
A common feature of all of the embodiments is that preferably at least 50 mol % of the radicals (A—O) are ethoxy radicals, in particular 60 to 90 mol % are ethoxy radicals. The number of propoxy and butoxy radicals is, in a preferred embodiment, at most so great that the cloud point of the compound of the formula 1 in water is still at 30° C. or above.
If X is N[(A—O)m—R], then the compounds of the formula 1 have the following structure:
Figure US06391923-20020521-C00004
The compounds of the formula 2, in which k, A, m, n, b and R are as defined above, are also provided by the invention.
The invention further provides compounds of the formula 1 in which X=O and R=C1-C4-alkyl. Preferably, in such compounds n=0.
The compounds of the formula 1 are also referred to below as polymerizable macromonomers.
The preparation of the polymerizable macromonomers, and illustrative applications of the dispersions according to the invention are described in more detail below and illustrated by reference to examples.
The polymerizable macromonomers are prepared by anion/alkali initiated polymerization of hydroxy- or amino-functional allyl or vinyl ethers (ethers which still have at least one active hydrogen atom) with alkylene oxide or mixtures of alkylene oxides in random distribution or as block copolymers. Furthermore, the resulting macromonomers can also be etherified at the terminal hydroxyl groups by means of a Williamson synthesis. The hydroxy- or amino-functional allyl or vinyl ethers have formula 3
Figure US06391923-20020521-C00005
where Y=OH, NH2.
The degree of water solubility, defined by the cloud point, of the polymerizable macromonomers, and the extent of their hydrophilicizing and dispersing action can be set by the ratio and number of alkylene oxide units, preferably of ethylene oxide to propylene oxide, and through the choice of the hydroxy- or amino-functional allyl or vinyl ether.
The free-radical initiated copolymerization of the polymerizable macromonomers with olefinically unsaturated water-insoluble monomers produces the copolymer dispersions according to the invention. Suitable water-insoluble monomers which can be polymerized with the macromonomers are, for example, the following:
vinyl monomers, such as carboxylic esters of vinyl alcohol, for example vinyl acetate, vinyl propionate, vinyl ether of isononanoic acid or of isodecanoic acid, styrene and stilbene,
olefinically unsaturated carboxylic esters, such as ethyl acrylate, n-butyl acrylate, i-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, and the corresponding methacrylic esters,
olefinically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid and itaconic acid and their sodium, potassium and ammonium salts,
olefinically unsaturated sulfonic acids and phosphonic acids and their alkali metal and ammonium salts, such as acrylamidomethylpropanesulfonic acid (AMPS) and its alkali metal and ammonium, alkylammonium and hydroxyalkylammonium salts, allylsulfonic acid and its alkali metal and ammonium salts, acryloyloxethylphosphonic acid and its ammonium and alkali metal salts, and the corresponding methacrylic acid derivatives,
olefinically unsaturated amines, ammonium salts, nitriles and amides, such as dimethylaminoethyl acrylate, acryloyloxethyltrimethylammonium halides, acrylonitrile, N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, and the corresponding methacrylic acid derivatives and vinylmethylacetamide,
olefins, such as ethylene, propene and butenes, pentene, 3-butadiene and chloroprene,
vinyl halides, such as vinyl chloride, vinylidene chloride and vinylidene fluoride.
The present invention further relates to the use of the above-defined macromonomers of the formula 1 in emulsion polymerizations or suspension polymerizations.
The invention further provides for the use of the polymerizable polyalkylene macromonomers according to the invention as emulsifiers or dispersants.
The compounds of the formula 1 can be used in suspension or emulsion polymerizations alone as emulsifiers, and also in a mixture with anionic and/or nonionic surfactants known in the prior art.
Customary anionic surfactants are sodium alkyl sulfate, sodium dodecylbenzenesulfonate, sodium alkylsulfonate, sodium and ammonium alkylpolyethylene glycol ether sulfates, sodium and ammonium alkylphenol polyethylene glycol ether sulfates, and alkylpolyethylene glycol ether phosphoric mono-, di- and triesters and mixtures thereof, and alkylphenol polyethylene glycol ether phosphoric mono-, di- and triesters and mixtures thereof.
EXAMPLES
The examples below illustrate the invention in more detail.
Example 1
50.5 g of 4-hydroxybutyl vinyl ether were adjusted to a pH of 14 using 0.2 mol NaOCH3 solution, and reacted with 440 g of ethylene oxide at superatmospheric pressure at 140° C. for 8 h. The resulting product (macromonomer) was completely water-soluble, i.e. the cloud point of the macromonomer in water is above 100° C. The OH number is 62.8 mg/KOH/g, corresponding to a molecular weight of 894 g/mol. This corresponds to a polyethylene oxide monobutyl vinyl ether having 18 units of ethylene oxide per vinyl ether unit. Using 1H-NMR and by determining the iodine number (21 g/100 g) it was possible to detect the total receipt of vinyl units (polymerizable units) per molecule.
Example 2
50.5 g of 4-hydroxybutyl vinyl ether were adjusted to a pH of 14 using 0.2 mol NaOCH3 solution and firstly reacted with 145 g of propylene oxide at superatmospheric pressure at 140° C. for 6 h. 440 g of ethylene oxide were added to the reaction product, and the mixture was likewise reacted at superatmospheric pressure at 140° C. for 8 h. The resulting product (macromonomer) was still completely water-soluble at room temperature, exhibited a cloud point in water of 64.4°0 C. and had surfactant, emulsifying properties. The OH number was 50.9 mg/KOH/g, corresponding to a molecular weight of 1100 g/mol. This corresponds to a polyethylene oxide-polypropylene oxide block copolymer monobutyl vinyl ether having 18 units of ethylene oxide and 4 units of propylene oxide per vinyl ether unit. Using 1H-NMR and by determining the iodine number (21 g/100 g) it was possible to detect the total receipt of vinyl units (polymerizable units) per molecule.
Example 3
50.5 g of diethylene glycol monovinyl ether were adjusted to a pH of 14 using 0.2 mol NaOCH3 solution, and reacted with 440 g of ethylene oxide at superatmospheric pressure at 140° C. for 8 h. The resulting product (macromonomer) was completely water-soluble, i.e. the cloud point of the macromonomer in water is above 100° C.
Example 4
50.5 g of aminopropyl vinyl ether were, adjusted to a pH of 14 using 0.1 mol NaOCH3 solution, and reacted with 440 g of ethylene oxide at superatmospheric pressure at 140° C. for 8 h. The resulting product (macromonomer) was completely water-soluble, i.e. the cloud point of the macromonomer in water is above 100° C.
Example 5
49.5 g of diethylene glycol monovinyl ether were adjusted to a pH of 14 using 0.1 mol NaOCH3 solution, and reacted with 800 g of ethylene oxide at superatmospheric pressure at 140° C. for 10 h. The resulting product (macromonomer) was completely water-soluble, i.e. the cloud point was above 100° C. The OH number was 28 mg/KOH/g, corresponding to a molecular weight of 2000 g/mol. Using 1H-NMR and by determining the iodine number (10 g/100 g) it was possible to detect the total receipt of vinyl units (polymerizable units) per molecule.
Example 6
The macromonomer from Example 1 is copolymerized with AMPS.
Example 7
The macromonomer from Example 2 is used as coemulsifier in the emulsion polymerization of vinyl acetate and vinyl isodecanoate. The copolymer of vinyl acetate and vinyl isodecanoate and the macromonomer from Example 2 which forms in situ has good emulsion-stabilizing properties because of its ambivalent structure.
360 ml of water are charged to a glass flask, and 6 g of ®Emulsogen EPA 073 (alkyl ether sulfate), 24 g of ®Tylose H 200 YG4 (hydroxyethylcellulose), 6 g of borax, 2.6 g of acetic acid (99% strength) and 92 g of a 1.17% strength potassium peroxodisulfate solution and 170 g of a monomer emulsion, which consists of 480 g of water, 6 g of Emulsogen EPA 073, 17 g of Emulsogen EPN 287 (alkyl ethoxylate), 30 g of the macromonomer from, Example 2, 300 g of vinyl isodecanoate and 900 g of vinyl acetate, are added. The mixture is then heated up to 76° C. and, after the reaction has started at 80° C., the remaining monomer emulsion and a further 210 g of a 1.17% strength ,potassium peroxodisulfate solution are metered in over 3 hours. The mixture is then stirred for 2 hours for after polymerization at 80° C. and cooled to room temperature. During the cooling phase, 3 g of preservative (200 Mergal K9N) are added.
Example 8
The macromonomer from Example 2 is used as coemulsifier in the emulsion polymerization of n-butyl acrylate, methyl methacrylate and methacrylic acid. The copolymer of n-butyl acrylate, methyl methacrylate and methacrylic acid and the macromonomer from Example 2 which forms in situ has good emulsion-stabilizing properties on the basis of its ambivalent structure.
520 ml of water are charged to a glass flask, and 16 g of ®Emulsogen EPA 1954 (sodium alkyl sulfate), 15 g of a 3.75% strength ammonium peroxodisulfate solution, 11.8 g of n-butyl acrylate, 11.8 g of methyl methacrylate and 0.48 g of methacrylic acid are added, and the mixture is stirred. The emulsion is heated to 80° C. with stirring and a monomer emulsion, which consists of 475 ml of water, 16 g of Emulsogen EPA 1954, 4.8 g of the macromonomer from Example 2, 440 g of n-butyl acrylate, 440 g of methyl methacrylate, 8.8 g of methacrylic acid and 2.85 g of ammonium peroxodisulfate is metered in over 4 hours. When all of the monomer emulsion has been metered in and following an afterpolymerization of one hour at 80° C., the polymer dispersion is cooled to room temperature and adjusted to pH 8-9 using ammonia solution.
Example 9
The macromonomer consisting of a block polymer of allyl alcohol, Which has been reacted firstly with 5 mol of propylene oxide and then with 30 mol of ethylene oxide, is used as coemulsifier in the emulsion polymerization of n-butyl acrylate, methyl methacrylate and methacrylic acid. The copolymer of n-butyl acrylate, methyl methacrylate and methacrylic acid and the described allyl alkoxide which forms in situ has good emulsion-stabilizing properties on the basis of its ambivalent structure.
520 ml of water are charged to a glass flask, and 16 g of ®Emulsogen EPA 1954 (sodium alkyl sulfate), 15 g of a 3.75% strength ammonium peroxodisulfate solution, 11.8 g of n-butyl acrylate, 11.8 g of methyl methacrylate and 0.48 g of methacrylic acid are added, and the mixture is stirred. The emulsion is heated to 80° C. with stirring, and a monomer emulsion which consists of 460 ml of water, 32 g of Emulsogen EPA 1954, 4.8 g of the described allyl alkoxylate, 440 g of n-butyl acrylate, 440 g of methyl methacrylate, 8.8 g of methacrylic acid and 2.85 g of ammonium peroxodisulfate, is metered in over 4 hours. When all of the monomer emulsion has been metered in and following an afterpolymerization of one hour at 80° C., the polymer dispersion is cooled to room temperature and adjusted to pH 8-9 using ammonia solution.
Example 10
To 100 g of the product from Example 1 are added, under nitrogen, firstly 10 g of solid NaOH, and then 14 g of n-butyl chloride are metered in. The reaction vessel is stirred at superatmospheric pressure for 5 hours at 80° C. The vessel is then evacuated and heated under reduced pressure to 120° C. and stirred for a further 3 hours.
After the reaction mixture has cooled, it is repeatedly stirred with 500 ml of water and left to stand to enable the phases to separate. The aqueous sodium-chloride-containing phase is discarded in each case. The upper phase (yield: 94 g/88%) is, according to 1H-NMR, iodine number determination (24 g/100 g) and OH number measurement (5 mg/g), finally the mono-n-butylpolyethylene glycol mono-4-hydroxyvinyl ether having 18 units of ethylene oxide.
Example 11
To 100 g of the product from Example 1 are added, under nitrogen in an autoclave, firstly 10 g of solid NaOH, and then 7 g of methyl chloride are metered in under superatmospheric pressure. The reaction vessel is stirred at superatmospheric pressure for 5 hours at 80° C. The vessel is then evacuated and heated under reduced pressure to 120° C. and stirred for a further 3 hours.
After the reaction mixture has cooled, it is repeatedly stirred with 500 ml of water and left to stand to enable the phases to separate. The aqueous sodium-chloride-containing phase is discarded in each case. The upper phase (yield: 92 g/90%) is, according to 1H-NMR, iodine number determination (26 g/100 g) and OH number measurement (5 mg/g), finally the mono-methyl polyethylene glycol mono4-hydroxyvinyl ether having 18 units of ethylene oxide.

Claims (9)

What is claimed is:
1. An aqueous dispersion preparable by polymerization of an olefinically unsaturated, water-insoluble compound in the presence of a water-soluble allyl, or vinyl ether of the formula 1
Figure US06391923-20020521-C00006
in which
b is 0 or 1
n is 0 or 1
k is an integer from 1to 20,
X is O or N[(A—O )m—R]
A is C2-C4-alkylene
m is an integer from 5 to 900, and
R is H or C1-C4-alkyl,
and in which A is not exclusively C3- or C4-alkylene, by mixing the olefinically unsaturated water-insoluble compound with the water-soluble allyl or vinyl ether in water, and triggering the polymerization by a free-radical initiator.
2. The aqueous dispersion as claimed in claim 1, in which k is a number from 4 to 8.
3. The aqueous dispersion as claimed in claim 1, in which X is oxygen.
4. The aqueous dispersion as claimed in claim 1, in which R is hydrogen.
5. The aqueous dispersion as claimed in claim 1, in which A is ethylene or propylene.
6. The aqueous dispersion as claimed in claim 1, in which —(A—O)m— is an alkylene oxide block polymer of the formula
Figure US06391923-20020521-C00007
in which
a is a number from 0 to 300,
b is a number from 5 to 300,
c is a number from 0 to 300.
7. The aqueous dispersion as claimed in claim 1, in which —(A—O)m— is an ethoxy chain having from 8 to 240 ethoxy units.
8. The aqueous dispersion as claimed in claim 6, wherein
a is a number from 1 to 80,
b is a number from 8 to 80, and
c is a number from 1 to 80.
9. The aqueous dispersion as claimed in claim 6, wherein
a is a number from 2 to 35,
b is a number from 10 to 45, and
c is a number from 8 to 35.
US09/615,422 1999-07-13 2000-07-13 Aqueous polymer dispersion, its preparation and use Expired - Fee Related US6391923B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10/103,903 US20020103290A1 (en) 1999-07-13 2002-03-22 Aqueous polymer dispersion, its preparation and use

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19932572 1999-07-13
DE19932572 1999-07-13
DE19939266A DE19939266B4 (en) 1999-07-13 1999-08-19 Aqueous polymer dispersion, its preparation and use
DE19939266 1999-08-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/103,903 Division US20020103290A1 (en) 1999-07-13 2002-03-22 Aqueous polymer dispersion, its preparation and use

Publications (1)

Publication Number Publication Date
US6391923B1 true US6391923B1 (en) 2002-05-21

Family

ID=26054154

Family Applications (2)

Application Number Title Priority Date Filing Date
US09/615,422 Expired - Fee Related US6391923B1 (en) 1999-07-13 2000-07-13 Aqueous polymer dispersion, its preparation and use
US10/103,903 Abandoned US20020103290A1 (en) 1999-07-13 2002-03-22 Aqueous polymer dispersion, its preparation and use

Family Applications After (1)

Application Number Title Priority Date Filing Date
US10/103,903 Abandoned US20020103290A1 (en) 1999-07-13 2002-03-22 Aqueous polymer dispersion, its preparation and use

Country Status (3)

Country Link
US (2) US6391923B1 (en)
EP (1) EP1069139A3 (en)
JP (1) JP2001064332A (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020103290A1 (en) * 1999-07-13 2002-08-01 Clariant Gmbh Aqueous polymer dispersion, its preparation and use
US20020186288A1 (en) * 2001-03-23 2002-12-12 Canon Kabushiki Kaisha Composition containing stimuli-responsive polymer, ink composition containing it, and image-forming method and apparatus using the ink composition
US20030124261A1 (en) * 2001-12-21 2003-07-03 Clariant Gmbh Olefinically unsaturated ether carboxylic acids and their use in emulsion polymerization
US20030171483A1 (en) * 2002-03-06 2003-09-11 Masayuki Ikegami Composition containing polymer having ionic functional group, ink composition, and image-forming method and image-forming apparatus employing the ink composition
US20030236343A1 (en) * 2002-04-26 2003-12-25 Koichi Sato Polymerizable compound, polymer compound and block polymer compound, and composition, image-forming method and image-forming apparatus using the same
US20040024090A1 (en) * 2002-07-03 2004-02-05 Sakae Suda Polymer composition, image-forming method and image-forming apparatus
US20050027037A1 (en) * 2002-03-06 2005-02-03 Koichi Sato Polymerizable compound, polymer compound composition using such compound, and image forming method and apparatus
US20070270510A1 (en) * 2006-03-30 2007-11-22 Liu Leo Z Reactive surfactants and their use in emulsions and dispersions
US20070270508A1 (en) * 2006-03-30 2007-11-22 Liu Leo Z Reactive monomeric surfactants
US20090312460A1 (en) * 2008-06-16 2009-12-17 Lorenz Klaus K Copolymer Admixture System for Workability Retention of Cementitious Compositions
US20100216968A1 (en) * 2007-10-25 2010-08-26 Basf Se Process for the preparation of polyether alcohols from unsaturated starters having active hydrogen atoms
US20100331510A1 (en) * 2009-05-20 2010-12-30 Basf Se Hydrophobically associating copolymers
US20110054083A1 (en) * 2008-02-13 2011-03-03 Klaus Lorenz Copolymer Comprising Polyether Side Chains and Hydroxyalkyl and Acid Structural Units
US20120029131A1 (en) * 2009-03-24 2012-02-02 Cognis Ip Management Gmbh Use Of Nonionic Surfactants As Emulsifiers For Emulsion Polymerization (III)
US20120157655A1 (en) * 2010-12-17 2012-06-21 Nippon Shokubai Co, Ltd Polyalkylene glycol-based polymer and process for producing the same
US9181373B2 (en) 2011-07-22 2015-11-10 Kuraray Co., Ltd. Polyoxyalkylene modified vinyl alcohol-based polymer and use thereof
US9284395B2 (en) 2012-12-11 2016-03-15 Construction Research & Technology Gmbh Continuous process for preparing copolymers
US10030088B2 (en) 2014-07-09 2018-07-24 Basf Se Reactive monomers as comonomers for the production of polymers
US10040987B2 (en) 2013-04-08 2018-08-07 S.P.C.M. Sa Polymers for enhanced hydrocarbon recovery

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018557A1 (en) * 2002-08-22 2004-03-04 Idemitsu Petrochemical Co., Ltd. α-OLEFIN POLYMER COMPOSITIONS AND PROCESS FOR PRODUCTION THEREOF
EP1717259A1 (en) * 2005-04-30 2006-11-02 Clariant Produkte (Deutschland) GmbH Copolymerisable polyalkylene glycol macromonomers , their preparation and their use
KR20070121451A (en) * 2006-06-22 2007-12-27 삼성전자주식회사 Method for preparing toner and toner prepared by using the method
DE102006048017B4 (en) 2006-10-09 2018-10-04 Basf Se Process for the preparation of polyether alcohols from unsaturated starters with active hydrogen atoms
DE102006049381A1 (en) * 2006-10-19 2008-04-24 Süd-Chemie AG Amphiphilic graft polymers
DE102006049804A1 (en) * 2006-10-23 2008-04-24 Clariant International Limited Preparing water-soluble block alkoxylates of unsaturated carboxylic acids, for use as emulsion stabilizing comonomers, by reacting acid successively with propylene and ethylene oxides
JP5705834B2 (en) 2009-05-20 2015-04-22 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Water-soluble copolymer having hydrophobic groups
EP3240854A4 (en) * 2014-12-31 2018-08-15 Kemira Oyj Emulsions containing alkyl ether sulfates and uses thereof
JP2019516694A (en) * 2016-05-11 2019-06-20 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Aqueous agricultural composition with improved scatter drift performance
JP6114868B1 (en) * 2016-09-29 2017-04-12 第一工業製薬株式会社 Surfactant composition
WO2020084046A1 (en) 2018-10-26 2020-04-30 Basf Se Process for preparing propylenoxy-containing hydrophobically associating monomers by dmc catalysis
WO2020084033A1 (en) 2018-10-26 2020-04-30 Basf Se Hydrophobically associating copolymers for enhanced oil recovery, comprising monomers with propylenoxy units

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05209052A (en) 1991-07-19 1993-08-20 Asahi Glass Co Ltd Polyether macromer and its polymer
EP0736553A2 (en) 1995-04-07 1996-10-09 SKW Trostberg Aktiengesellschaft Copolymers based on oxyalkyleneglycol alkenyl ethers and derivatives of unsaturated dicarboxylic acids
EP0870784A1 (en) 1997-04-07 1998-10-14 Cement Intellectual Property Ltd. Acrylic copolymers

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3052652A (en) * 1958-02-26 1962-09-04 Borden Co Alkoxylated polyvinyl alcohol
NL238305A (en) * 1958-04-21
US3027339A (en) * 1958-10-03 1962-03-27 Ciba Ltd Unsaturated esters of aminotriazine formaldehyde condensation products
US3183281A (en) * 1961-07-19 1965-05-11 Rohm & Haas Stable self-catalyzing epoxy resin compositions
US5849840A (en) * 1986-11-07 1998-12-15 Nippon Gohsei Kagaku Kogyo Kabushiki Kaisha Dispersing stabilizer
JP2621308B2 (en) * 1987-03-13 1997-06-18 日本油脂株式会社 Allyl ether-maleic anhydride copolymer
AU607072B2 (en) * 1988-05-24 1991-02-21 Asahi Glass Company Limited Fluorine-containing copolymer, process for its production and curable composition
DE3901608A1 (en) * 1989-01-20 1990-07-26 Byk Chemie Gmbh COATINGS AND MOLDINGS CONTAINING POLYMERISES OF ALKYLVINYL ETHERS AND THEIR USE AS EXPORTING OR ANTI-CLAIMING AGENTS
US5514288A (en) * 1993-12-28 1996-05-07 Basf Corporation Method of pretreating fabrics to impart soil release properties thereto using polymers of vinyl ethers
JPH09316370A (en) * 1996-05-30 1997-12-09 Denki Kagaku Kogyo Kk Magnetic substance particle and magnetic recording medium
US5912284A (en) * 1996-12-26 1999-06-15 Nippon Shokubai Co., Ltd. Cement additive, its production process and use
EP1069139A3 (en) * 1999-07-13 2003-03-12 Clariant GmbH Aqueous polymer dispersion, its preparation and use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05209052A (en) 1991-07-19 1993-08-20 Asahi Glass Co Ltd Polyether macromer and its polymer
EP0736553A2 (en) 1995-04-07 1996-10-09 SKW Trostberg Aktiengesellschaft Copolymers based on oxyalkyleneglycol alkenyl ethers and derivatives of unsaturated dicarboxylic acids
US5798425A (en) * 1995-04-07 1998-08-25 Skw Trostberg Aktiengesellschaft Co-polymers based on oxyalkyleneglycol alkenyl ethers and unsaturated dicarboxylic acid derivatives
EP0870784A1 (en) 1997-04-07 1998-10-14 Cement Intellectual Property Ltd. Acrylic copolymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
W.P. J. Bailey in Chemistry and Technology of water soluble Polymers, Plenum Press, 1983, p. 261-265.

Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020103290A1 (en) * 1999-07-13 2002-08-01 Clariant Gmbh Aqueous polymer dispersion, its preparation and use
US7056972B2 (en) * 2001-03-23 2006-06-06 Canon Kabushiki Kaisha Composition containing stimuli-responsive polymer, ink composition containing it, and image-forming method and apparatus using the ink composition
US20020186288A1 (en) * 2001-03-23 2002-12-12 Canon Kabushiki Kaisha Composition containing stimuli-responsive polymer, ink composition containing it, and image-forming method and apparatus using the ink composition
US20030124261A1 (en) * 2001-12-21 2003-07-03 Clariant Gmbh Olefinically unsaturated ether carboxylic acids and their use in emulsion polymerization
US7378480B2 (en) * 2002-03-06 2008-05-27 Canon Kabushiki Kaisha Polymerizable compound, polymer compound, composition using such compound, and image forming method and apparatus
US7291668B2 (en) 2002-03-06 2007-11-06 Canon Kabushiki Kaisha Composition containing polymer having ionic functional group, ink composition, and image-forming method and image-forming apparatus employing the ink composition
US20050027037A1 (en) * 2002-03-06 2005-02-03 Koichi Sato Polymerizable compound, polymer compound composition using such compound, and image forming method and apparatus
US20050272834A1 (en) * 2002-03-06 2005-12-08 Canon Kabushiki Kaisha Composition containing polymer having ionic functional group, ink composition, and image-forming method and image-forming apparatus employing the ink composition
US20030171483A1 (en) * 2002-03-06 2003-09-11 Masayuki Ikegami Composition containing polymer having ionic functional group, ink composition, and image-forming method and image-forming apparatus employing the ink composition
US7037996B2 (en) * 2002-03-06 2006-05-02 Canon Kabushiki Kaisha Composition containing polymer having ionic functional group, ink composition, and image-forming method and image-forming apparatus employing the ink composition
US7491780B2 (en) 2002-04-26 2009-02-17 Canon Kabushiki Kaisha Polymerizable compound, polymer compound and block polymer compound, and composition, image-forming method and image-forming apparatus using the same
US7157539B2 (en) * 2002-04-26 2007-01-02 Canon Kabushiki Kaisha Polymerizable compound, polymer compound and block polymer compound, and composition, image-forming method and image-forming apparatus using the same
US20030236343A1 (en) * 2002-04-26 2003-12-25 Koichi Sato Polymerizable compound, polymer compound and block polymer compound, and composition, image-forming method and image-forming apparatus using the same
US20050277728A1 (en) * 2002-04-26 2005-12-15 Koichi Sato Polymerizable compound, polymer compound and block polymer compound, and composition, image-forming method and image-forming apparatus using the same
US7381759B2 (en) * 2002-07-03 2008-06-03 Canon Kabushiki Kaisha Polymer composition, image-forming method and image-forming apparatus
US20040024090A1 (en) * 2002-07-03 2004-02-05 Sakae Suda Polymer composition, image-forming method and image-forming apparatus
US20070270510A1 (en) * 2006-03-30 2007-11-22 Liu Leo Z Reactive surfactants and their use in emulsions and dispersions
US20070270508A1 (en) * 2006-03-30 2007-11-22 Liu Leo Z Reactive monomeric surfactants
US20090163650A1 (en) * 2006-03-30 2009-06-25 Rhodia Inc. Reactive surfactants and their use in emulsions and dispersions
US7585927B2 (en) * 2006-03-30 2009-09-08 Rhodia Inc. Reactive surfactants and their use in emulsions and dispersions
US8354488B2 (en) * 2006-03-30 2013-01-15 Rhodia Operations Reactive surfactants and their use in emulsions and dispersions
US8119733B2 (en) 2006-03-30 2012-02-21 Rhodia Operations Reactive monomeric surfactants
US20100216968A1 (en) * 2007-10-25 2010-08-26 Basf Se Process for the preparation of polyether alcohols from unsaturated starters having active hydrogen atoms
CN101835822B (en) * 2007-10-25 2012-06-27 巴斯夫欧洲公司 Process for preparing polyether alcohols from unsaturated starters with active hydrogen atoms
US8399608B2 (en) 2007-10-25 2013-03-19 Basf Aktiengesellschaft Process for the preparation of polyether alcohols from unsaturated starters having active hydrogen atoms
US20110054083A1 (en) * 2008-02-13 2011-03-03 Klaus Lorenz Copolymer Comprising Polyether Side Chains and Hydroxyalkyl and Acid Structural Units
US8519030B2 (en) 2008-02-13 2013-08-27 Construction Research & Technology Gmbh Copolymer comprising polyether side chains and hydroxyalkyl and acid structural units
US8519029B2 (en) 2008-06-16 2013-08-27 Construction Research & Technology Gmbh Copolymer admixture system for workability retention of cementitious compositions
US7973110B2 (en) 2008-06-16 2011-07-05 Construction Research & Technology Gmbh Copolymer synthesis process
US20090312504A1 (en) * 2008-06-16 2009-12-17 Lorenz Klaus K Copolymer Synthesis Process
US8242218B2 (en) 2008-06-16 2012-08-14 Construction Research & Technology Gmbh Copolymer synthesis process
US20090312460A1 (en) * 2008-06-16 2009-12-17 Lorenz Klaus K Copolymer Admixture System for Workability Retention of Cementitious Compositions
US20120029131A1 (en) * 2009-03-24 2012-02-02 Cognis Ip Management Gmbh Use Of Nonionic Surfactants As Emulsifiers For Emulsion Polymerization (III)
US8779075B2 (en) * 2009-03-24 2014-07-15 Cognis Ip Management Gmbh Use of nonionic surfactants as emulsifiers for emulsion polymerization (III)
US8783356B2 (en) 2009-05-20 2014-07-22 Basf Se Hydrophobically associating copolymers
US8362180B2 (en) 2009-05-20 2013-01-29 Basf Se Hydrophobically associating copolymers
US20100331510A1 (en) * 2009-05-20 2010-12-30 Basf Se Hydrophobically associating copolymers
US9163103B2 (en) 2009-05-20 2015-10-20 Basf Se Hydrophobically associating copolymers
US8586687B2 (en) * 2010-12-17 2013-11-19 Nippon Shokubai Co., Ltd. Polyalkylene glycol-based polymer and process for producing the same
US20120157655A1 (en) * 2010-12-17 2012-06-21 Nippon Shokubai Co, Ltd Polyalkylene glycol-based polymer and process for producing the same
US9181373B2 (en) 2011-07-22 2015-11-10 Kuraray Co., Ltd. Polyoxyalkylene modified vinyl alcohol-based polymer and use thereof
US9284395B2 (en) 2012-12-11 2016-03-15 Construction Research & Technology Gmbh Continuous process for preparing copolymers
US10040987B2 (en) 2013-04-08 2018-08-07 S.P.C.M. Sa Polymers for enhanced hydrocarbon recovery
US10030088B2 (en) 2014-07-09 2018-07-24 Basf Se Reactive monomers as comonomers for the production of polymers

Also Published As

Publication number Publication date
EP1069139A2 (en) 2001-01-17
US20020103290A1 (en) 2002-08-01
JP2001064332A (en) 2001-03-13
EP1069139A3 (en) 2003-03-12

Similar Documents

Publication Publication Date Title
US6391923B1 (en) Aqueous polymer dispersion, its preparation and use
JP2652459B2 (en) Emulsifier for emulsion polymerization
US20050261457A1 (en) Copolymers made of alkylene oxides and glycidyl ethers and use thereof as polymerisable emulsifiers
EP0706535A1 (en) Processes for preparing aqueous polymer emulsions
JPH0616752A (en) Production of aqueous plastic dispersion
US20020045703A1 (en) Processes for preparing aqueous polymer emulsions
US7812114B2 (en) Block copolymer by reacting alkylene oxide and glycidyl ether in presence of unsaturated monomer
EP0107300B1 (en) Redox-initiated polymerisation process for the production of non-charged, wholly sterically stabilised aqueous polymer dispersions
IE54820B1 (en) Polymerisation process
US8142681B2 (en) Aqueous surfactant compositions with a low pour point
JP4385440B2 (en) Polymerizable polyoxyalkylene monoalkyl ether derivative, polymer of the derivative, and dispersant containing the polymer
JP2006505661A (en) Styrene oxide-containing copolymers and their use as emulsifiers and dispersants
WO2000020463A9 (en) Use of derivatives of polyaspartic acid as emulsifiers and stabilizers in aqueous free radical emulsion polymerization
JP4271849B2 (en) Polymerization method
EP0102707B1 (en) Process for production of sterically stabilised wholly non-charged aqueous polymer dispersions
JP2887551B2 (en) Emulsifier for emulsion polymerization
US20030124261A1 (en) Olefinically unsaturated ether carboxylic acids and their use in emulsion polymerization
US20040077774A1 (en) Alkyl and aryl alkoxylates as emulsifiers in emulsion polymerisation
JP4917279B2 (en) Emulsifier for emulsion polymerization
DE19939266B4 (en) Aqueous polymer dispersion, its preparation and use
JP4663934B2 (en) New phosphate ester type surfactant
JP3292551B2 (en) Emulsifier for emulsion polymerization
JPH0841113A (en) New reactive surfactant, emulsifier for emulsion polymerization, and resin modifier
JP4782481B2 (en) Emulsifier for emulsion polymerization
JP4160438B2 (en) Novel sulfate ester type surfactant

Legal Events

Date Code Title Description
AS Assignment

Owner name: CLARIANT GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:POLLMANN, KLAUS;AHRENS, HENDRIK;STANKOWIAK, ACHIM;REEL/FRAME:010952/0827;SIGNING DATES FROM 20000417 TO 20000425

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH, GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:CLARIANT GMBH;REEL/FRAME:018627/0100

Effective date: 20051128

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20100521